JP2005074331A - Surface treatment method and device manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a uniform contact angle without increasing the number of steps even when a plurality of types of functional liquids are used.
A functional liquid in which a film forming component is dissolved or dispersed in a medium is applied. Correlations between a plurality of types of liquid repellency treatments performed on the surface of the substrate P, a plurality of types of media, and a contact angle with respect to the functional liquid are obtained in advance. The type of liquid repellency treatment is selected based on the type of medium of the functional liquid applied to the substrate P, the desired contact angle, and the correlation. A step of applying the selected lyophobic treatment to the surface of the substrate P.
[Selection] Figure 3

Description

  The present invention relates to a surface treatment method and a device manufacturing method.

  2. Description of the Related Art Conventionally, a photolithography method has been frequently used as a method for manufacturing a fine wiring pattern such as a semiconductor integrated circuit. On the other hand, Patent Document 1, Patent Document 2, and the like disclose a method using a droplet discharge method. The techniques disclosed in these publications form a wiring pattern by disposing (applying) a material on a pattern forming surface by discharging a functional liquid containing a pattern forming material from a droplet discharge head onto a substrate. It is said to be very effective, such as being able to cope with a variety of small-volume production.

By the way, in recent years, the density of circuits constituting a device has been increased, and for example, further miniaturization and thinning of wiring patterns are required.
However, when such a fine wiring pattern is to be formed by the above-described method using the droplet discharge method, it is particularly difficult to sufficiently obtain the accuracy of the wiring width. For this reason, a method has been proposed in which a bank as a partitioning member is provided on the substrate, and a surface treatment is performed so that the upper part of the bank is liquid repellent and the other parts are lyophilic. Since it is formed using the lithography method, it leads to high cost.

Therefore, in Patent Document 3, a liquid repellent portion is formed on the substrate surface using an organic molecular film, and the organic molecular film is decomposed in a predetermined pattern by exposing it to an ultraviolet irradiation or an ozone atmosphere, and a desired contact angle. A technique for selectively applying a liquid (functional liquid) in which conductive fine particles are dispersed to the lyophilic part is disclosed. In this case, for example, the liquid material in which the conductive fine particles are dispersed easily collects in the lyophilic portion. Therefore, the conductive film pattern can be formed while maintaining the accuracy of the wiring width without forming a bank.
Japanese Patent Laid-Open No. 11-274671 JP 2000-216330 A JP 2002-164635 A

However, the following problems exist in the conventional technology as described above.
When forming a film pattern using a plurality of types of ink (functional liquid) on a substrate, or when forming a film pattern using a medium such as a different type of solvent or dispersion medium even with the same conductive fine particles, a particularly large size is required. When a substrate is used, the contact angle may be uneven.
In addition, in order to obtain a desired contact angle uniformly, it may be possible to set conditions for post-treatment (ultraviolet irradiation, exposing the substrate to an ozone atmosphere) according to each ink. In this case, however, the number of steps increases. Cause the problem.

  The present invention has been made in consideration of the above points. A surface treatment method and a device manufacturing method capable of obtaining a uniform contact angle without increasing the number of steps even when a plurality of types of functional liquids are used. The purpose is to provide.

In order to achieve the above object, the present invention employs the following configuration.
The surface treatment method of the present invention is a surface treatment method for a substrate to which a functional liquid obtained by dissolving or dispersing a film-forming component in a medium is applied, and includes a plurality of types of liquid repellency treatments applied to the substrate surface and a plurality of types. The correlation between the medium and the contact angle with respect to the functional liquid is obtained in advance, and the liquid repellent treatment is performed based on the type of medium of the functional liquid applied to the substrate, the desired contact angle, and the correlation. The method includes a step of selecting a type and applying the selected lyophobic treatment to the surface of the substrate.

Therefore, in the present invention, since the surface of the substrate exhibits a desired contact angle with respect to the functional liquid, it is not necessary to separately perform the lyophilic process after the liquid repellent process, and the number of processes can be reduced. In the present invention, since the liquid repellent process is performed according to the medium of the functional liquid, the liquid repellent process corresponding to each medium is selected even when, for example, a functional liquid of a different type of medium is applied on a large substrate. By applying, a uniform contact angle can be obtained for a plurality of types of functional liquids.
As the liquid repellent treatment, a treatment for forming a self-assembled film made of a compound having a fluoroalkyl group on the surface of the substrate can be employed.
In this case, since each compound is oriented so that the fluoroalkyl group is located on the surface of the film to form a self-assembled film, uniform liquid repellency is imparted to the surface of the film.

In addition, when the liquid repellent treatment having the desired contact angle does not exist in the correlation obtained in advance, it is preferable to select a type of liquid repellent treatment that exhibits a contact angle larger than the desired contact angle.
When the lyophobic treatment with a contact angle smaller than the desired contact angle is performed, the functional liquid applied on the substrate wets and spreads to increase the line width, but in the present invention, the substrate surface is larger than the desired contact angle. In order to develop a large contact angle, the functional liquid applied on the substrate has a line width smaller than a desired width. Therefore, in this case, a desired line width can be obtained by applying the functional liquid a plurality of times.

On the other hand, the device manufacturing method of the present invention includes a step of surface-treating a substrate by the surface treatment method described above, and a step of discharging droplets of the functional liquid onto the surface-treated substrate. It is what.
Thus, in the present invention, even when a device is manufactured by discharging a plurality of types of functional liquid droplets having different types of media onto the substrate, a uniform and desired contact angle is obtained without performing lyophilic treatment. be able to. Therefore, it is possible to obtain a device having a uniform pattern with a desired line width without increasing the number of steps.

In the present invention, it is also possible to employ a procedure in which the liquid repellency treatment and the droplet ejection are repeated a plurality of times.
Thereby, for example, even when a pattern is formed over a plurality of layers with a plurality of types of functional liquids having different types of media, a uniform pattern having a desired line width can be obtained without performing a lyophilic process.

Hereinafter, embodiments of the surface treatment method and the device manufacturing method of the present invention will be described with reference to FIGS.
(First embodiment)
In the present embodiment, a wiring pattern (thin film pattern) ink (functional liquid) containing conductive fine particles is ejected in droplets from a nozzle of a liquid ejection head by a droplet ejection method, and formed on a substrate with a conductive film. A description will be given by using an example of forming a wiring pattern.

First, the wiring pattern ink which is a functional liquid will be described.
Wiring pattern ink ejected in droplets from a nozzle of a liquid ejection head by a droplet ejection method is generally composed of a dispersion liquid in which conductive fine particles are dispersed in a dispersion medium (medium) as a film forming component.
In the present embodiment, as the conductive fine particles, for example, metal fine particles containing any one of gold, silver, copper, palladium, and nickel, these oxides, and fine particles of conductive polymers and superconductors. Etc. are used.
These conductive fine particles can be used by coating the surface with an organic substance or the like in order to improve dispersibility.
The particle diameter of the conductive fine particles is preferably 1 nm or more and 0.1 μm or less. If it is larger than 0.1 μm, there is a possibility that clogging may occur in the nozzle of the liquid discharge head described later. On the other hand, if it is smaller than 1 nm, the volume ratio of the coating agent to the conductive fine particles becomes large, and the ratio of the organic matter in the obtained film becomes excessive.

  The dispersion medium is not particularly limited as long as it can disperse the conductive fine particles and does not cause aggregation. For example, in addition to water, alcohols such as methanol, ethanol, propanol, butanol, n-heptane, n-octane, decane, dodecane, tetradecane, toluene, xylene, cymene, durene, indene, dipentene, tetrahydronaphthalene, decahydro Hydrocarbon compounds such as naphthalene and cyclohexylbenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 1,2-dimethoxyethane, bis (2- Methoxyethyl) ether, ether compounds such as p-dioxane, propylene carbonate, γ- Butyrolactone, N- methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, can be exemplified polar compounds such as cyclohexanone. Of these, water, alcohols, hydrocarbon compounds, and ether compounds are preferred from the viewpoints of fine particle dispersibility and dispersion stability, and ease of application to the droplet discharge method (inkjet method). More preferred dispersion media include water and hydrocarbon compounds.

  The surface tension of the conductive fine particle dispersion is preferably in the range of 0.02 N / m to 0.07 N / m. When the liquid is ejected by the ink jet method, if the surface tension is less than 0.02 N / m, the wettability of the ink composition to the nozzle surface increases, and thus flight bending tends to occur, exceeding 0.07 N / m. Since the meniscus shape at the nozzle tip is not stable, it becomes difficult to control the discharge amount and the discharge timing. In order to adjust the surface tension, a small amount of a surface tension regulator such as a fluorine-based, silicone-based, or nonionic-based material may be added to the dispersion within a range that does not significantly reduce the contact angle with the substrate. The nonionic surface tension modifier improves the wettability of the liquid to the substrate, improves the leveling property of the film, and helps prevent the occurrence of fine irregularities in the film. The surface tension modifier may contain an organic compound such as alcohol, ether, ester, or ketone, if necessary.

  The viscosity of the dispersion is preferably 1 mPa · s to 50 mPa · s. When a liquid material is ejected as droplets using the inkjet method, if the viscosity is less than 1 mPa · s, the nozzle periphery is easily contaminated by the outflow of the ink, and if the viscosity is greater than 50 mPa · s, the nozzle hole The clogging frequency of the liquid becomes high, and it becomes difficult to smoothly discharge the droplets.

  Various substrates such as glass, quartz glass, Si wafer, plastic film, and metal plate can be used as the substrate on which the wiring pattern is formed. Also included are those in which a semiconductor film, a metal film, a dielectric film, an organic film or the like is formed as a base layer on the surface of these various material substrates.

Here, examples of the discharge technique of the droplet discharge method include a charge control method, a pressure vibration method, an electromechanical conversion method, an electrothermal conversion method, and an electrostatic suction method. In the charge control method, a charge is applied to a material by a charging electrode, and the flight direction of the material is controlled by a deflection electrode and discharged from a nozzle. In addition, the pressurized vibration method is a method in which an ultra-high pressure of about 30 kg / cm ² is applied to the material and the material is discharged to the nozzle tip side. When no control voltage is applied, the material goes straight and is discharged from the nozzle. When a control voltage is applied, electrostatic repulsion occurs between the materials, and the materials are scattered and are not discharged from the nozzle. The electromechanical conversion method utilizes the property that a piezoelectric element (piezoelectric element) is deformed by receiving a pulse-like electric signal. The piezoelectric element is deformed through a flexible substance in a space where material is stored. Pressure is applied, and the material is extruded from this space and discharged from the nozzle.

  In the electrothermal conversion method, a material is rapidly vaporized by a heater provided in a space in which the material is stored to generate bubbles, and the material in the space is discharged by the pressure of the bubbles. In the electrostatic attraction method, a minute pressure is applied in a space in which the material is stored, a meniscus of the material is formed on the nozzle, and an electrostatic attractive force is applied in this state before the material is drawn out. In addition to this, techniques such as a system that uses a change in the viscosity of a fluid due to an electric field and a system that uses a discharge spark are also applicable. The droplet discharge method has an advantage that the use of the material is less wasteful and a desired amount of the material can be accurately disposed at a desired position. The amount of one drop of the liquid material (fluid) discharged by the droplet discharge method is, for example, 1 to 300 nanograms.

Next, a device manufacturing apparatus used when manufacturing a device according to the present invention will be described.
As this device manufacturing apparatus, a droplet discharge apparatus (inkjet apparatus) that manufactures a device by discharging droplets from a droplet discharge head onto a substrate is used.

FIG. 1 is a perspective view showing a schematic configuration of the droplet discharge device IJ.
The droplet discharge device IJ includes a droplet discharge head 1, an X-axis direction drive shaft 4, a Y-axis direction guide shaft 5, a control device CONT, a stage 7, a cleaning mechanism 8, a base 9, and a heater. 15.
The stage 7 supports the substrate P on which ink (functional liquid) is provided by the droplet discharge device IJ, and includes a fixing mechanism (not shown) that fixes the substrate P to a reference position.

  The droplet discharge head 1 is a multi-nozzle type droplet discharge head including a plurality of discharge nozzles, and the longitudinal direction and the Y-axis direction are made to coincide. The plurality of ejection nozzles are provided on the lower surface of the droplet ejection head 1 at regular intervals along the Y-axis direction. From the ejection nozzle of the droplet ejection head 1, the ink containing the conductive fine particles described above is ejected onto the substrate P supported by the stage 7.

An X-axis direction drive motor 2 is connected to the X-axis direction drive shaft 4. The X-axis direction drive motor 2 is a stepping motor or the like, and rotates the X-axis direction drive shaft 4 when a drive signal in the X-axis direction is supplied from the control device CONT. When the X-axis direction drive shaft 4 rotates, the droplet discharge head 1 moves in the X-axis direction.
The Y-axis direction guide shaft 5 is fixed so as not to move with respect to the base 9. The stage 7 includes a Y-axis direction drive motor 3. The Y-axis direction drive motor 3 is a stepping motor or the like, and moves the stage 7 in the Y-axis direction when a drive signal in the Y-axis direction is supplied from the control device CONT.

The control device CONT supplies the droplet discharge head 1 with a voltage for controlling droplet discharge. In addition, a drive pulse signal for controlling the movement of the droplet discharge head 1 in the X-axis direction is supplied to the X-axis direction drive motor 2, and a drive pulse signal for controlling the movement of the stage 7 in the Y-axis direction is sent to the Y-axis direction drive motor 3. Supply.
The cleaning mechanism 8 cleans the droplet discharge head 1. The cleaning mechanism 8 is provided with a Y-axis direction drive motor (not shown). By driving the drive motor in the Y-axis direction, the cleaning mechanism moves along the Y-axis direction guide shaft 5. The movement of the cleaning mechanism 8 is also controlled by the control device CONT.
Here, the heater 15 is a means for heat-treating the substrate P by lamp annealing, and performs evaporation and drying of the solvent contained in the liquid material applied on the substrate P. The heater 15 is also turned on and off by the control device CONT.

  The droplet discharge device IJ discharges droplets onto the substrate P while relatively scanning the droplet discharge head 1 and the stage 7 that supports the substrate P. Here, in the following description, the X-axis direction is a scanning direction, and the Y-axis direction orthogonal to the X-axis direction is a non-scanning direction. Therefore, the discharge nozzles of the droplet discharge head 1 are provided at regular intervals in the Y-axis direction, which is the non-scanning direction. In FIG. 1, the droplet discharge head 1 is arranged at a right angle to the traveling direction of the substrate P, but the angle of the droplet discharging head 1 is adjusted so as to intersect the traveling direction of the substrate P. It may be. In this way, the pitch between the nozzles can be adjusted by adjusting the angle of the droplet discharge head 1. Further, the distance between the substrate P and the nozzle surface may be arbitrarily adjusted.

FIG. 2 is a diagram for explaining the principle of discharging a liquid material by a piezo method.
In FIG. 2, a piezo element 22 is installed adjacent to a liquid chamber 21 for storing a liquid material (wiring pattern ink, functional liquid). The liquid material is supplied to the liquid chamber 21 via a liquid material supply system 23 including a material tank that stores the liquid material. The piezo element 22 is connected to a drive circuit 24, and a voltage is applied to the piezo element 22 via the drive circuit 24 to deform the piezo element 22, whereby the liquid chamber 21 is deformed and the liquid material is discharged from the nozzle 25. Is discharged. In this case, the amount of distortion of the piezo element 22 is controlled by changing the value of the applied voltage. Further, the strain rate of the piezo element 22 is controlled by changing the frequency of the applied voltage. Since the droplet discharge by the piezo method does not apply heat to the material, it has an advantage of hardly affecting the composition of the material.

Next, as an example of an embodiment of the device manufacturing method of the present invention, a method for forming a conductive film wiring on a substrate (a thin film pattern forming method) will be described with reference to FIG. In the wiring pattern forming method according to the present embodiment, the wiring pattern ink described above is disposed on the substrate P, and a conductive film pattern (conductive film) for wiring is formed on the substrate P. It is roughly composed of a processing step, a material placement step, and a heat treatment / light treatment step.
Hereinafter, each process will be described in detail.

  In this example, the above-described wiring pattern ink of the present invention is used as the conductive film wiring ink. In addition, for the arrangement of ink, a droplet discharge method in which ink is discharged as droplets via the nozzle 25 of the liquid discharge head 1 using a droplet discharge device IJ, a so-called inkjet method is used. Here, as a discharge method of the droplet discharge device, in addition to the piezo method, a method of discharging a liquid material when vapor is rapidly generated by application of heat may be used.

(Surface treatment process)
In the surface treatment process, the surface of the substrate on which the conductive film wiring is formed is subjected to a surface treatment selected according to the liquid material (functional liquid) to be used to make the liquid repellent (liquid repellent treatment process). In addition, the selected liquid repellency treatment has been obtained in advance through experiments or the like, and a correlation between a plurality of types of dispersion medium and the contact angle with respect to the functional liquid is obtained for a plurality of types. Select as appropriate.
As a method for controlling the liquid repellency (wetting property) of the surface, for example, a method of forming a self-assembled film on the surface of the substrate can be employed.

In the self-assembled film forming method, a self-assembled film made of an organic molecular film or the like is formed on the surface of a substrate on which conductive film wiring is to be formed.
The organic molecular film for treating the substrate surface has a functional group that can bind to the substrate and a functional group that modifies the surface properties of the substrate, such as a lyophilic group or a liquid repellent group, on the opposite side (controls the surface energy). And a carbon straight chain or a partially branched carbon chain connecting these functional groups, and is bonded to a substrate and self-assembles to form a molecular film, for example, a monomolecular film.

  Here, the self-assembled film is composed of a binding functional group capable of reacting with constituent atoms such as an underlayer of the substrate and other linear molecules, and has extremely high orientation due to the interaction of the linear molecules. It is a film formed by orienting a compound. Since this self-assembled film is formed by orienting single molecules, the film thickness can be extremely reduced, and the film is uniform at the molecular level. That is, since the same molecule is located on the surface of the film, uniform and excellent liquid repellency can be imparted to the surface of the film.

By using, for example, fluoroalkylsilane as the compound having high orientation, each compound is oriented so that the fluoroalkyl group is located on the surface of the film, and a self-assembled film is formed. Liquid repellency is imparted.
Examples of compounds that form a self-assembled film include heptadecafluoro-1,1,2,2 tetrahydrodecyltriethoxysilane, heptadecafluoro-1,1,2,2 tetrahydrodecyltrimethoxysilane, heptadecafluoro-1 , 1,2,2 tetrahydrodecyltrichlorosilane, tridecafluoro-1,1,2,2 tetrahydrooctyltriethoxysilane, tridecafluoro-1,1,2,2 tetrahydrooctyltrimethoxysilane, tridecafluoro-1 , 1,2,2 tetrahydrooctyltrichlorosilane, trifluoropropyltrimethoxysilane, and other fluoroalkylsilanes (hereinafter referred to as “FAS”). These compounds may be used alone or in combination of two or more. Note that by using FAS, adhesion to the substrate and good liquid repellency can be obtained.

FAS is generally represented by the structural formula RnSiX _(4-n) . Here, n represents an integer of 1 to 3, and X is a hydrolyzable group such as a methoxy group, an ethoxy group, or a halogen atom. R is a fluoroalkyl group, and has a structure of (CF ₃ ) (CF ₂ ) x (CH ₂ ) y (where x represents an integer of 0 to 10 and y represents an integer of 0 to 4). And when a plurality of R or X are bonded to Si, each R or X may be the same or different. The hydrolyzable group represented by X forms silanol by hydrolysis, reacts with the hydroxyl group of the base of the substrate (glass, silicon), and bonds to the substrate with a siloxane bond. On the other hand, since R has a fluoro group such as (CF ₂ ) on the surface, the base surface of the substrate is modified to a surface that does not get wet (surface energy is low).

A self-assembled film made of an organic molecular film or the like is formed on a substrate by placing the above raw material compound and the substrate in the same sealed container and leaving them at room temperature for about 2 to 3 days. Further, by holding the entire sealed container at 100 ° C., it is formed on the substrate in about 3 hours. These are formation methods from the gas phase, but a self-assembled film can also be formed from the liquid phase. For example, the self-assembled film is formed on the substrate by immersing the substrate in a solution containing the raw material compound, washing, and drying.
Note that before the self-assembled film is formed, it is desirable to pre-treat the substrate surface by irradiating the substrate surface with ultraviolet light or washing with a solvent.

In addition, the process which processes the surface of the board | substrate P to liquid repellency is the film which has liquid repellency according to the dispersion medium to be used and a desired contact angle, for example, the polyimide film etc. which were processed with the tetrafluoroethylene on the board | substrate surface You may also go by sticking. Moreover, you may use a polyimide film with high liquid repellency as a board | substrate as it is.
As described above, by performing the self-organizing film forming method, the liquid repellent film F is formed on the surface of the substrate P as shown in FIG.

(Material placement process)
Next, the wiring pattern forming material is applied to a predetermined position on the substrate P by using the droplet discharge method by the droplet discharge apparatus IJ. Here, as a functional liquid (wiring pattern ink), a dispersion liquid in which conductive fine particles are dispersed in a solvent (dispersion medium) is discharged. The conductive fine particles used here include fine particles of conductive polymer or superconductor in addition to metal fine particles containing any of gold, silver, copper, palladium, and nickel.

  That is, in the material arranging step, the wiring pattern forming material is supplied from the liquid ejection head 1 as shown in FIG. 3B while relatively moving the droplet ejection head 1 and the substrate P of the above-described droplet ejection apparatus IJ. The contained liquid material is discharged as droplets 32, and the droplets 32 are arranged at predetermined positions on the substrate P. Specifically, a linear wiring pattern is formed by discharging a plurality of droplets 32 at a predetermined pitch while relatively moving the droplet discharge head 1 and the substrate P along the wiring pattern formation direction. To do.

(Heat treatment / light treatment process)
Next, in the heat treatment / light treatment step, the dispersion medium or the coating agent contained in the droplets disposed on the substrate is removed. That is, the liquid material for forming a conductive film disposed on the substrate needs to completely remove the dispersion medium in order to improve electrical contact between the fine particles. Further, when a coating agent such as an organic substance is coated on the surface of the conductive fine particles in order to improve dispersibility, it is also necessary to remove this coating agent.

The heat treatment and / or light treatment is usually performed in the air, but may be performed in an inert gas atmosphere such as nitrogen, argon, or helium as necessary. The treatment temperature of the heat treatment and / or the light treatment depends on the boiling point (vapor pressure) of the dispersion medium, the type and pressure of the atmospheric gas, the thermal behavior such as the dispersibility and oxidation of the fine particles, the presence and amount of the coating agent, It is determined appropriately in consideration of the heat resistant temperature.
For example, in order to remove the coating agent made of organic matter, it is necessary to bake at about 300 ° C. Moreover, when using a board | substrate, such as a plastics, it is preferable to carry out at room temperature or more and 100 degrees C or less.

The heat treatment and / or light treatment may be performed using lamp annealing in addition to general heat treatment using a heating means such as a hot plate or an electric furnace. The light source used for lamp annealing is not particularly limited, but excimer laser such as infrared lamp, xenon lamp, YAG laser, argon laser, carbon dioxide laser, XeF, XeCl, XeBr, KrF, KrCl, ArF, ArCl, etc. Can be used. These light sources generally have a power output in the range of 10 W to 5000 W, but in the present embodiment, a range of 100 W to 1000 W is sufficient.
By the heat treatment and / or light treatment, electrical contact between the fine particles is ensured and converted into a conductive film as shown in FIG.
Through the series of steps described above, a linear conductive film pattern (conductive film wiring) is formed on the substrate.

(Example)
Subsequently, the present invention will be specifically described with reference to (Table 1).

予め実験により、複数種の撥液性膜（ここでは上述したＦＡＳ）と複数種の分散媒（例えば炭化水素系のテトラデカン、ドデカン、デカン）と、これら各分散媒、撥液性膜に対応する接触角及びドット径（１０ｐｌ吐出時）との相関関係を求めておく（表１参照）。
ここではＦＡＳとして、上記フルオロアルキル基においてｘ＝０のもの（以下、ＦＡＳ３と称する）、及びｘ＝７のもの（以下、ＦＡＳ１７と称する）について実験を行った。

According to experiments, a plurality of types of liquid repellent films (herein, the FAS described above), a plurality of types of dispersion media (for example, hydrocarbon-based tetradecane, dodecane, decane), and the respective dispersion media and liquid repellent films are supported. The correlation between the contact angle and the dot diameter (at the time of 10 pl discharge) is obtained (see Table 1).
Here, as FAS, an experiment was performed on the fluoroalkyl group having x = 0 (hereinafter referred to as FAS3) and x = 7 (hereinafter referred to as FAS17).

For example, when a functional liquid of a tetradecane medium is used and a droplet is applied onto a substrate with a dot diameter of 40 μm, FAS 17 is selected from the correlation shown in Table 1, and a functional liquid of a dodecane medium is used and a liquid with a dot diameter of 65 μm is selected. When droplets are applied on the substrate, FAS 3 is selected from the correlation shown in Table 1, and the surface treatment for forming the selected liquid repellent film is performed on the substrate.
Further, when pattern formation is performed on the same substrate using the functional liquid of each medium, for example, substrate cleaning → liquid repellency treatment (FAS3 formation) → drawing with functional liquid of dodecane medium (pattern formation) → intermediate drying The process may be performed in the following order: overlay drawing → main firing → liquid repellent treatment (formation of FAS 17) → drawing with a functional liquid of tetradecane medium (pattern formation) → intermediate drying → overlay drawing → main firing.
In addition, when drawing with the functional liquid of a tetradecane medium, it may be overlaid on the pattern formed with the functional liquid of the dodecane medium, or may be drawn on another place on the same substrate. The order of drawing with the functional liquid of the dodecane medium and drawing with the functional liquid of the tetradecane medium may be reversed.

Thus, in the present embodiment, a desired contact angle can be obtained by the liquid repellent film, so that it is not necessary to perform a lyophilic process such as ultraviolet irradiation after the conventional liquid repellent process, and the number of processes can be reduced. It becomes possible to reduce.
In this embodiment, since the heat resistance of the FAS is not impaired by not performing the lyophilic process, the contact angle does not change even when heating is performed during intermediate drying, and the pattern formation accuracy is improved. Is also possible.
Furthermore, in this embodiment, since the liquid repellency process is performed according to each medium based on the correlation obtained in advance, even when a pattern is formed using a plurality of types of functional liquids with different media, On the other hand, a uniform desired contact angle can be obtained, and a device having a pattern with a predetermined line width can be manufactured.

(Second Embodiment)
In the first embodiment, the liquid repellent film (liquid repellency process) corresponding to the medium to be used and the desired contact angle exists, but the corresponding liquid repellency process may not exist in the correlation obtained in advance. . For example, when the contact angle is set to 50 [deg] using a tetradecane medium, there is no corresponding liquid repellent film in Table 1.
In such a case, in the present embodiment, a lyophobic process for expressing a contact angle larger than a desired contact angle is performed. Specifically, FAS 17 described in Table 1 is selected, and surface treatment for forming a film on the substrate is performed.
When the film is formed by selecting FAS3, the dot diameter becomes large and a pattern having a predetermined line width cannot be formed. However, in the present embodiment, a desired dot is formed on the substrate by forming FAS17. A droplet having a diameter smaller than the diameter is formed. Therefore, it is possible to form a pattern with a desired line width by performing droplet discharge a plurality of times so that the droplets overlap.

(Third embodiment)
In the first and second embodiments described above, the FAS is used as the liquid-repellent film. However, even with other liquid-repellent films (and media), a plurality of types of media, contact angles, and liquid-repellent properties are previously stored. If the correlation with the conductive film is obtained, an appropriate liquid repellent treatment can be selected according to the medium to be used and the desired contact angle.
Table 2 shows an example of these correlations.

この表に示されるように、ここでは媒体（分散媒）としてＨ_２Ｏ、ヘキサデカン、ＤＭＩ（1,3-ジメチル-2-イミダゾリジノン）、ＥＧ（エチレングリコール）を用い、撥液性膜として、アルキルアミン（CH_３（CH_２）_１７NH_２及びCH_３（CH_２）_１１NH_２）、アルキルシラン（CH_３（CH_２）_９Si）及びアルキル基における直鎖の水素を一部フッ素に置換したもの（CF_３（CF_２）_７（CH_２）_２Si）を用いた場合の接触角との相関関係を求めている。
本実施の形態でも、表２に示される媒体を用いる場合において、所望の接触角に応じた撥液性膜（撥液化処理）を選択することで、工程数を減らすことができるとともに、複数種類の機能液を用いる場合でも均一な接触角を得ることが可能になる。

As shown in this table, here, H ₂ O, hexadecane, DMI (1,3-dimethyl-2-imidazolidinone), EG (ethylene glycol) is used as a medium (dispersion medium), and a liquid repellent film is used. , Alkylamine (CH ₃ (CH ₂ ) ₁₇ NH ₂ and CH ₃ (CH ₂ ) ₁₁ NH ₂ ), alkylsilane (CH ₃ (CH ₂ ) ₉ Si), and linear hydrogen in the alkyl group partially into fluorine The correlation with the contact angle in the case of using a substituted one (CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si) is obtained.
Also in this embodiment, when the medium shown in Table 2 is used, the number of steps can be reduced and a plurality of types can be selected by selecting a liquid repellent film (liquid repellent treatment) according to a desired contact angle. Even when the functional liquid is used, a uniform contact angle can be obtained.

(Fourth embodiment)
As a fourth embodiment, a liquid crystal display device which is an example of an electro-optical device provided with a device manufactured by the device manufacturing method of the present invention will be described. FIG. 4 is a plan view of the liquid crystal display device as seen from the counter substrate side shown together with each component, and FIG. 5 is a cross-sectional view taken along the line HH ′ of FIG. FIG. 6 is an equivalent circuit diagram of various elements and wirings in a plurality of pixels formed in a matrix in the image display region of the liquid crystal display device, and FIG. 7 is a partial enlarged cross-sectional view of the liquid crystal display device. In each drawing used in the following description, the scale is different for each layer and each member so that each layer and each member can be recognized on the drawing.

  4 and 5, the liquid crystal display device (electro-optical device) 100 according to the present embodiment has a TFT array substrate 10 and a counter substrate 20 that are paired with a sealing material 52 that is a photo-curable sealing material. The liquid crystal 50 is sealed and held in the region partitioned by the sealing material 52. The sealing material 52 is formed in a frame shape that is closed in a region within the substrate surface, does not include a liquid crystal injection port, and does not have a trace sealed with the sealing material.

  A peripheral parting 53 made of a light shielding material is formed in a region inside the region where the sealing material 52 is formed. A data line driving circuit 201 and a mounting terminal 202 are formed along one side of the TFT array substrate 10 in a region outside the sealing material 52, and the scanning line driving circuit 204 is formed along two sides adjacent to the one side. Is formed. On the remaining side of the TFT array substrate 10, a plurality of wirings 205 are provided for connecting between the scanning line driving circuits 204 provided on both sides of the image display area. Further, at least one corner of the counter substrate 20 is provided with an inter-substrate conductive material 206 for establishing electrical continuity between the TFT array substrate 10 and the counter substrate 20.

Instead of forming the data line driving circuit 201 and the scanning line driving circuit 204 on the TFT array substrate 10, for example, a TAB (Tape Automated Bonding) substrate on which a driving LSI is mounted and a peripheral portion of the TFT array substrate 10 The terminal group formed in the above may be electrically and mechanically connected via an anisotropic conductive film. In the liquid crystal display device 100, depending on the type of the liquid crystal 50 to be used, that is, depending on the operation mode such as TN (Twisted Nematic) mode, STN (Super Twisted Nematic) mode, or normally white mode / normally black mode. A retardation plate, a polarizing plate, and the like are arranged in a predetermined direction, but the illustration is omitted here.
Further, when the liquid crystal display device 100 is configured for color display, in the counter substrate 20, for example, red (R), green (G), A blue (B) color filter is formed together with the protective film.

  In the image display region of the liquid crystal display device 100 having such a structure, as shown in FIG. 6, a plurality of pixels 100a are arranged in a matrix, and each of these pixels 100a has a pixel switching region. TFT (switching element) 30 is formed, and a data line 6 a for supplying pixel signals S 1, S 2,..., Sn is electrically connected to the source of the TFT 30. Pixel signals S1, S2,..., Sn to be written to the data lines 6a may be supplied line-sequentially in this order, or may be supplied for each group to a plurality of adjacent data lines 6a. . Further, the scanning line 3a is electrically connected to the gate of the TFT 30, and the scanning signals G1, G2,..., Gm are applied to the scanning line 3a in a pulse-sequential manner in this order at a predetermined timing. It is configured.

  The pixel electrode 19 is electrically connected to the drain of the TFT 30, and the pixel signal S1, S2,..., Sn supplied from the data line 6a is obtained by turning on the TFT 30 as a switching element for a certain period. Write to each pixel at a predetermined timing. The pixel signals S1, S2,..., Sn written in the liquid crystal through the pixel electrode 19 in this way are held for a certain period with the counter electrode 121 of the counter substrate 20 shown in FIG. In order to prevent the held pixel signals S1, S2,..., Sn from leaking, a storage capacitor 60 is added in parallel with the liquid crystal capacitor formed between the pixel electrode 19 and the counter electrode 121. For example, the voltage of the pixel electrode 19 is held by the storage capacitor 60 for a time that is three orders of magnitude longer than the time when the source voltage is applied. Thereby, the charge retention characteristics are improved, and the liquid crystal display device 100 with a high contrast ratio can be realized.

FIG. 7A is a partial enlarged cross-sectional view of a liquid crystal display device 100 having a bottom gate type TFT 30. On the glass substrate P constituting the TFT array substrate 10, the device manufacturing method described in the above embodiment is used. A gate wiring 61 is formed.
A semiconductor layer 63 made of an amorphous silicon (a-Si) layer is stacked on the gate wiring 61 with a gate insulating film 62 made of SiNx interposed therebetween. A portion of the semiconductor layer 63 facing the gate wiring portion is a channel region. On the semiconductor layer 63, junction layers 64a and 64b made of, for example, an n + -type a-Si layer for obtaining an ohmic junction are stacked, and the channel is protected on the semiconductor layer 63 in the central portion of the channel region. An insulating etch stop film 65 made of SiNx is formed. The gate insulating film 62, the semiconductor layer 63, and the etch stop film 65 are patterned as shown in the figure by performing resist coating, photosensitive / developing, and photoetching after vapor deposition (CVD).

  Further, the bonding layers 64a and 64b and the pixel electrode 19 made of ITO are formed in the same manner, and are patterned as shown in the figure by performing photoetching. Banks 66 are provided on the pixel electrode 19, the gate insulating film 62, and the etch stop film 65, and silver droplets are discharged between the banks 66 using the above-described droplet discharge device IJ. Thus, a source line and a drain line can be formed.

As shown in FIG. 7B, a recess is provided in the gate insulating film 62, a semiconductor layer 63 is formed in the recess substantially flush with the surface of the gate insulating film 62, and a bonding layer 64a is formed thereon. 64b, the pixel electrode 19, and the etch stop film 65 can also be formed. In this case, by making the groove bottom between the banks 66 substantially flat as compared with FIG. 7A, the bent portions of these layers, the source line and the drain line are reduced, and the flatness is improved. can do.
In the TFT having the above-described configuration, a gate line, a source line, a drain line, and the like can be formed by ejecting, for example, silver compound droplets using the above-described droplet ejection device IJ. Even in the case of discharging, a high-quality liquid crystal display device having a small number of steps and a uniform contact angle and improved line width accuracy can be obtained.

(Fifth embodiment)
In the above embodiment, the TFT 30 is used as a switching element for driving the liquid crystal display device 100. However, the present invention can be applied to, for example, an organic EL (electroluminescence) display device in addition to the liquid crystal display device. An organic EL display device has a structure in which a thin film containing a fluorescent inorganic and organic compound is sandwiched between a cathode and an anode, and is excited by injecting electrons and holes into the thin film and recombining them. It is an element that emits light by using light emission (fluorescence / phosphorescence) when a child (exciton) is generated and the exciton is deactivated. Then, on the substrate having the TFT 30 described above, among the fluorescent materials used for the organic EL display element, a material exhibiting each emission color of red, green and blue, that is, a light emitting layer forming material and a hole injection / electron transport layer are provided. A self-luminous full-color EL device can be manufactured by using ink as a material to be formed and patterning each.
The range of the device (electro-optical device) in the present invention includes such an organic EL device, and obtains a high-quality organic EL device with a reduced number of steps and a uniform contact angle and improved line width accuracy. Can do.

(Sixth embodiment)
Next, a plasma type display device which is an example of an electro-optical device will be described as a sixth embodiment.
FIG. 8 is an exploded perspective view of the plasma display device 500 of this embodiment.
The plasma display device 500 includes substrates 501 and 502 disposed opposite to each other, and a discharge display unit 510 formed therebetween.
The discharge display unit 510 is a collection of a plurality of discharge chambers 516. Among the plurality of discharge chambers 516, the three discharge chambers 516 of the red discharge chamber 516 (R), the green discharge chamber 516 (G), and the blue discharge chamber 516 (B) are arranged so as to form one pixel. Has been.

Address electrodes 511 are formed in stripes at predetermined intervals on the upper surface of the substrate 501, and a dielectric layer 519 is formed so as to cover the address electrodes 511 and the upper surface of the substrate 501. A partition wall 515 is formed on the dielectric layer 519 so as to be positioned between the address electrodes 511 and 511 and along the address electrodes 511. The barrier ribs 515 include barrier ribs adjacent to the left and right sides of the address electrode 511 in the width direction, and barrier ribs extending in a direction orthogonal to the address electrodes 511. A discharge chamber 516 is formed corresponding to a rectangular region partitioned by the partition 515.
In addition, a phosphor 517 is disposed inside a rectangular region defined by the partition 515. The phosphor 517 emits red, green, or blue fluorescence. The red phosphor 517 (R) is located at the bottom of the red discharge chamber 516 (R), and the bottom of the green discharge chamber 516 (G). Are arranged with a green phosphor 517 (G) and a blue phosphor 517 (B) at the bottom of the blue discharge chamber 516 (B).

On the other hand, a plurality of display electrodes 512 are formed in stripes at predetermined intervals on the substrate 502 in a direction orthogonal to the previous address electrodes 511. Further, a dielectric layer 513 and a protective film 514 made of MgO or the like are formed so as to cover them.
The substrate 501 and the substrate 502 are bonded to each other with the address electrodes 511... And the display electrodes 512.
The address electrode 511 and the display electrode 512 are connected to an AC power supply (not shown). By energizing each electrode, the phosphor 517 emits light in the discharge display portion 510, and color display is possible.

  In the present embodiment, since the address electrode 511 and the display electrode 512 are formed based on the above-described device manufacturing method, high-quality plasma with fewer steps and improved line width accuracy with a uniform contact angle. A mold display device can be obtained.

(Seventh embodiment)
Subsequently, an embodiment of a non-contact card medium will be described as a seventh embodiment. As shown in FIG. 9, a non-contact card medium (electronic device) 400 according to the present embodiment includes a semiconductor integrated circuit chip 408 and an antenna circuit 412 in a housing formed of a card base 402 and a card cover 418. At least one of power supply and data transmission / reception is performed by at least one of electromagnetic waves and capacitive coupling with an external transceiver (not shown).

In the present embodiment, the antenna circuit 412 is formed by the device manufacturing method according to the embodiment.
According to the non-contact type card medium of the present embodiment, it is possible to obtain a high-quality non-contact type card medium having a small number of steps and a uniform contact angle and improved line width accuracy.
In addition to the above, the device (electro-optical device) according to the present invention utilizes a phenomenon in which electron emission is caused by flowing a current through a small-area thin film formed on a substrate in parallel to the film surface. The present invention can also be applied to a surface conduction electron-emitting device.

(Eighth embodiment)
As an eighth embodiment, a specific example of an electronic device of the present invention will be described.
FIG. 10A is a perspective view showing an example of a mobile phone. In FIG. 10A, reference numeral 600 denotes a mobile phone body, and reference numeral 601 denotes a liquid crystal display unit including the liquid crystal display device of the above embodiment.
FIG. 10B is a perspective view illustrating an example of a portable information processing apparatus such as a word processor or a personal computer. In FIG. 10B, reference numeral 700 denotes an information processing device, 701 denotes an input unit such as a keyboard, 703 denotes an information processing body, and 702 denotes a liquid crystal display unit including the liquid crystal display device of the above embodiment.
FIG. 10C is a perspective view illustrating an example of a wristwatch type electronic device. In FIG. 10C, reference numeral 800 denotes a watch body, and reference numeral 801 denotes a liquid crystal display unit including the liquid crystal display device of the above embodiment.
Since the electronic apparatus shown in FIGS. 10A to 10C includes the liquid crystal display device of the above-described embodiment, it can be downsized, thinned, and improved in quality.
In addition, although the electronic device of this embodiment shall be provided with a liquid crystal device, it can also be set as the electronic device provided with other electro-optical devices, such as an organic electroluminescent display apparatus and a plasma type display apparatus.

  The preferred embodiments of the present invention have been described above with reference to the accompanying drawings, but it goes without saying that the present invention is not limited to such examples. Various shapes, combinations, and the like of the constituent members shown in the above-described examples are examples, and various modifications can be made based on design requirements and the like without departing from the gist of the present invention.

  In the above embodiment, the functional liquid composed of a dispersion liquid in which conductive fine particles are dispersed in a dispersion medium is used. However, the present invention is not limited to this, and a liquid organometallic compound or organometallic compound is not limited thereto. A solution may be used. Examples of the organometallic compound include compounds and complexes containing, for example, gold, silver, copper, palladium, and the like, and a metal is deposited by thermal decomposition. Specifically, chlorotriethylphosphine gold (I), chlorotrimethylphosphine gold (I), chlorotriphenylphosphine gold (I), silver (I) 2,4-pentanedionate complex, trimethylphosphine (hexafluoroacetylacetonate ) Silver (I) complex, copper (I) hexafluoropentanediotocyclooctadiene complex, and the like. As the solvent, the above-described dispersion medium can be used. Further, as the functional liquid, for example, a material that exhibits conductivity by heating (heat treatment) or light irradiation (light treatment) after pattern formation may be used.

It is a schematic perspective view of a droplet discharge device. It is a figure for demonstrating the discharge principle of the liquid material by a piezo method. It is a figure which shows the procedure which forms a wiring pattern. It is the top view which looked at the liquid crystal display device from the counter substrate side. It is sectional drawing which follows the H-H 'line | wire of FIG. It is an equivalent circuit diagram of a liquid crystal display device. It is a partial expanded sectional view of a liquid crystal display device. It is a disassembled perspective view of a plasma type display apparatus. It is a disassembled perspective view of a non-contact type card medium. It is a figure which shows the specific example of an electronic device.

Explanation of symbols

P ... substrate, 32 ... droplet

Claims (5)

A surface treatment method for a substrate to which a functional liquid obtained by dissolving or dispersing a film-forming component in a medium is applied,
Finding in advance a correlation between a plurality of types of liquid repellent treatment applied to the substrate surface, a plurality of types of the medium, and a contact angle with respect to the functional liquid,
Select the type of liquid repellent treatment based on the type of medium of the functional liquid applied to the substrate, the desired contact angle, and the correlation,
A surface treatment method comprising a step of applying a selected lyophobic treatment to the surface of the substrate. The surface treatment method according to claim 1,
A type of lyophobic treatment that causes a contact angle larger than the desired contact angle to be expressed when the lyophobic treatment with the desired contact angle does not exist in the correlation obtained in advance is selected. Surface treatment method. The surface treatment method according to claim 1 or 2,
The surface treatment method, wherein the lyophobic treatment is a treatment of forming a self-assembled film made of a compound having a fluoroalkyl group on the surface of the substrate. Applying the surface treatment to the substrate by the surface treatment method according to claim 1;
Discharging droplets of the functional liquid onto the surface-treated substrate;
A device manufacturing method comprising: The device manufacturing method according to claim 4,
A device manufacturing method, wherein the liquid repellency treatment and the discharge of the droplets are repeated a plurality of times.

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